Bridging the gap between mesoscopic and molecular models of solid/liquid interfaces out-of-equilibrium

TL;DR

This paper investigates the microscopic origins of mass transfer at solid/liquid interfaces out of equilibrium, using molecular simulations to connect atomistic details with mesoscale models, especially in electrolyte solutions with non-idealities.

Contribution

It introduces a strategy using CμMD simulations to quantify non-idealities at solid/liquid interfaces and links microscopic interactions to macroscopic mass transfer models.

Findings

Sodium ions preferentially adsorb at solid surfaces, causing local electroneutrality violations.

Electrochemical properties at interfaces deviate significantly from bulk fluid behavior.

The approach enhances understanding of non-idealities in electrolyte interface modeling.

Abstract

Solid/liquid interfaces control various processes of technological relevance in the process industry and many fundamental physicochemical phenomena. This work examines the link between the atomistic description of mass transfer at solid/liquid interfaces out of equilibrium and the constitutive mass transfer equations typically used to model these processes at the mesoscale. In our analysis, we discuss the microscopic inconsistencies apparent in simplified models of mass transfer whenever non-idealities dominate the liquid phase in the proximity of solid/liquid interfaces. Using C{\mu}MD - a molecular simulation technique to investigate out-of-equilibrium, concentration-driven processes with pseudo open-boundary conditions - we outline a strategy to capture and quantify non-idealities induced by specific interactions between the solid surface and molecules in the fluid phase. We demonstrate our approach by studying electrolyte solutions in technologically important, multi-component systems in which introducing a solid/liquid interface induces substantial deviations in the composition and electrochemical properties compared to the fluid phase bulk. To this aim, we analyse NaCl(aq) solutions in contact with i) the graphite basal surface and ii) {100} NaCl(s) crystalline surfaces. We uncover the tendency of the sodium cation to preferentially adsorb at the surfaces considered, which induces local violations of electroneutrality that leads to the emergence of an electric potential in the fluid phase at the solid/liquid interface.